CN101511788B - Eco-friendly process for recovery of pyridine and/or its derivatives - Google Patents
Eco-friendly process for recovery of pyridine and/or its derivatives Download PDFInfo
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- CN101511788B CN101511788B CN2006800558238A CN200680055823A CN101511788B CN 101511788 B CN101511788 B CN 101511788B CN 2006800558238 A CN2006800558238 A CN 2006800558238A CN 200680055823 A CN200680055823 A CN 200680055823A CN 101511788 B CN101511788 B CN 101511788B
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- pyridine
- acetate
- solvent
- water
- verivate
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 238000000034 method Methods 0.000 title claims abstract description 102
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000011084 recovery Methods 0.000 title abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- -1 alkyl acetate Chemical compound 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- 238000004064 recycling Methods 0.000 claims description 15
- 230000007613 environmental effect Effects 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 7
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 46
- 239000003960 organic solvent Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000000622 liquid--liquid extraction Methods 0.000 abstract description 5
- 238000000638 solvent extraction Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000008346 aqueous phase Substances 0.000 abstract description 2
- 231100001261 hazardous Toxicity 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- 238000000605 extraction Methods 0.000 description 22
- 239000010410 layer Substances 0.000 description 20
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 15
- 150000003222 pyridines Chemical class 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000003039 volatile agent Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000004508 fractional distillation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 101100008044 Caenorhabditis elegans cut-1 gene Proteins 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005373 pervaporation Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OENLEHTYJXMVBG-UHFFFAOYSA-N pyridine;hydrate Chemical compound [OH-].C1=CC=[NH+]C=C1 OENLEHTYJXMVBG-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-L ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-L 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009183 running Effects 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- MKMALRLAYRHGQJ-UHFFFAOYSA-N 3-methylpyridine;pyridine Chemical compound C1=CC=NC=C1.CC1=CC=CN=C1 MKMALRLAYRHGQJ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- AITBHTAFQQYBHP-UHFFFAOYSA-N benzene;pyridine Chemical compound C1=CC=CC=C1.C1=CC=NC=C1 AITBHTAFQQYBHP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
Disclosed herein is a process for recovery of pyridine and/or its derivatives from their aqueous mass and/ or manufacturing reaction mass by liquid-liquid extraction employing an environmentally non-hazardous organic solvent. The process further comprising effective recovering and recycle of solvents from the aqueous phase and the other waste obtained during the process.
Description
Technical field
Substantially, the present invention relates to the field of recovery of heterocyclic aromatic bases.More specifically, the present invention provide to eco-friendly from aqueous substance and/or make the method that RM reclaims pyridine and/or pyridine derivate, this method is at the liquid-liquid extraction of use down of the organic solvent of environmental sound.
Background technology
Pyridine and pyridine derivate are effectively as solvent and catalyzer.They use in many variant prodns synthetic, and this product is used as medicine, VITAMINs, flavorant, coating, dyestuff, rubber product, tackiness agent, sterilant and weedicide.
The industrial building-up reactions of the most common preparation pyridine bases is to use ammonia to pass through catalyzing and condensing aldehydes and/or ketone.This reaction usually in the presence of aluminium-silicate catalyst 350-500 ℃ with barometric point under carry out.Acetaldehyde, formaldehyde (with the Superlysoform form) and ammonia are added the reactor drum that contains catalyzer, wherein form pyridine and alkyl pyridine as primary product.Multiple catalyzer, reactant and reaction conditions were reported in the prior art." Pyridine and Pyridine Derivatives ", Goe, Gerald L, Kirk-Othmer, the 3rd edition, Vol.19, John Wiley&Sons, p.454 (1978); " Synthetic and Natural sources of the Pyridine Ring " in " Heterocyclic Compounds " the 14th volume; People such as Bailey, pp.1-252, " Pyridine and Its Derivatives "; John Wiley&Sons, New York (1984); With many other reference, it all is hereby incorporated by.
Through pyridine and the pyridine derivate that exists in the suitable method extraction aqueous substance.Several different methods has been applied to separate the problem of pyridine and pyridine derivate.Pyridine-water azeotropic mixture separates according to routine techniques, for example through add suitable solvent conventional destroy this water-pyridine azeotropic mixture then fractional distillation with the anhydrous basically pyridine of preparation.Through distillation solvent is recovered and recycled to regenerating column from pyridine.
Existing patent discloses several different methods and has been used for through using different solvents to separate pyridine or pyridine derivate from the aqueous solution.
The most often use benzene to come to reclaim pyridine and picoline from the water-based RM.Referring to the people such as " Pyridine and Pyridine Derivatives " Shimizu in the document " Ullman ' s Encyclopedia of Industrial Chemistry " p.399, Vol.A22, the 5th edition.; Elvers, B., Hawkins, S., Russey, W., Schulz, G., Eds., VCH Publishers, Weinheim (1993).
USP 4,883,881 disclose a kind of method, wherein through adding benzene pyridine are distilled the gained mixture to reclaim anhydrous basically pyridine then from pyridine-water azeotropic mixture separation.
Yet losing of benzene causes following concern in the method, such as expense, Occupational safety, the fire hazard of increase and the additional investment of harmful waste processing cost of environmental protective measure.In addition, because its harmful character, the use of benzene is forbidden in many industry.Therefore, be badly in need of addressing this problem, especially when this method when technical scale is carried out.
U.S. Patent number 2,058,435 have reported a kind of method, and wherein the aqueous solution of pyridine and its homologue extracts with efficient extraction agent, and the relative water of this extraction agent is non-solvent.This method comprises with any of multiple solvent such as benzene, trieline, isopropyl ether, pseudocumol (pseudo-cumene), hexanaphthene, hexane etc. and reclaims pyridine from its aqueous solution.
European patent number EP 1,346,757 discloses and has used the solvent of being made up of the fluorizated fluid to carry out liquid-liquid extraction, and this fluorizated fluid is selected from the mixture of hydrogen perfluoroalkyl polyether, hydrogen fluorine ether, hydrogen fluorine carbon and/or they and PFPE and/or perfluorocarbon.
Also can use other routine techniques, for example, drying operation, extraction, deposition, redistillation etc.; Consider according to conventional fully, for example, like what in any of a plurality of associated documents, discussed; For example, referring to document " Chemist ' s Companion ", Gordon; People such as Arnold J., John Wiley and Sons (1972).
Park, people such as Choon Ho. be at Journal of Applied Polymer Science (1999), and 74 (1), disclose among the 83-89 through vinyl cyanide-vinyl phosphonate co-polymer membrane pervaporation separation.Synthetic polyacrylonitrile (the PAN)-base co-polymer that contains the phosphonic acids part is to be used for the dehydration of pyridine solution.By the mixture that the pyridine original position in the vinyl phosphonate in the film (VP) part and the charging forms, strengthened the separating power of vinyl cyanide-vinyl phosphonic acid copolymer (PANVP) film.All contain phosphonic PAN-basement membrane has special selectivity to glassware for drinking water.The pervaporation performance of PANVP film depends on the content and the service temperature of phosphonic acids part in the film.Use PANVP film pervaporation separation of water/pyridine mixtures to show that water concentration infiltration and flow above 99.8% are 4-120gm
-2h
-1, this depends on the content and the service temperature of vinyl phosphonate.
U.S. Patent number 6,087,507 have described the method for separating pyridine or pyridine derivate continuously from the aqueous solution through extracting, and wherein use supercutical fluid (supercritical fluid) to extract the pyridine material from liquid medium.The method of this invention, the special carbonic acid gas that uses pressurization are from aqueous solution extraction pyridine or pyridine derivate, and this carbonic acid gas uses under pressure or is liquid state, or near criticality or be supercritical state.This os is successive operation extracting system, so that part or all of pyridine and/or pyridine derivate are transferred to the carbonic acid gas phase from water, and makes water mutually separated from one another with carbonic acid gas afterwards; And pyridine and/or pyridine derivate are from carbon dioxide separation; Thereby obtain to contain the extract of pyridine and/or pyridine derivate.The preferred temperature that pyridine and/or pyridine derivate contact with carbonic acid gas is 5 to 80 ℃; And preferred pressure is 60 to 300 crust.Yet this method is not suitable for technical scale, because extraction is carried out under very high pressure (60 to 300 crust).This makes that the extracting process operation is unfriendly and when technical scale, uses substantial contribution.
Disclosed method is used harmful and industrial inappropriate solvent in the prior art.Some disclosed solvents are handled very dangerous in plant-scale manufacturing processed.The problem that above-mentioned prior art is relevant can be through using industrial available; Exercisable and to the method for eco-friendly and solvent to avoid problems all in the above-mentioned prior art.
Summary of the invention
Therefore; An object of the present invention is to improve restriction of the prior art; Wherein the present invention provides from aqueous substance (aqueous mass) and/or makes the improved method that RM (manufacturing reaction mass) reclaims pyridine and/or its verivate; This method is at the liquid-liquid extraction of use down through the organic solvent selected, and it is an environmental sound.
Another purpose of the present invention provides the method that eco-friendly is used to reclaim pyridine and/or its verivate; Reclaim and the recycling solvent in other refuse that wherein this method obtains from organic phase, water and this method effectively, thereby method is had an economic benefit.
Another purpose of the present invention provides the method that eco-friendly is used to reclaim pyridine and/or its verivate; Wherein said method can be made RM from it and reclaim said pyridine and/or its verivate, and wherein said manufacturing RM comprises pyridine, β picoline, ammonia, aliphatic amine, aldehyde and aldehyde radical organic impurity, other monoalkyl pyridines, dialkyl group pyridines, trialkyl pyridines or Unidentified heavy organic substance.
Another purpose of the present invention provide to eco-friendly and have an economic benefit and be used to reclaim the method for pyridine and/or its verivate; Wherein said the object of the invention is through using suitable solvent and effectively handling with the solvent in recovery and the said method of recycling and realize; Said suitable solvent is an environmental sound, and it is selected from the Class III solvent according to the ICH guide.
Another purpose of the present invention is to select appropriate organic solvent and from the method for its water-based RM and/or its manufacturing RM recovery pyridine and/or its verivate, using this solvent through liquid-liquid extraction; The solvent phase ratio that wherein uses with prior art, said solvent be nontoxic, environmentally acceptable and with aqueous medium can be miscible.
These obtain according to following embodiment with other purpose, and following specific embodiments is described according to the preferred forms of practice, but the invention is not restricted to this specific embodiments.
According to the preferred embodiments of the invention; Provide eco-friendly is used for making the method that RM reclaims pyridine and/or its verivate from aqueous substance and/or its; This method comprises with organic solvent handles said material; Separating obtained organic phase and water; And distill said organic phase to obtain pyridine and/or its verivate and the said organic solvent of part, wherein distill other refuse that obtains in said water and this method and esterification to reclaim the also recycling in the method for said organic solvent again.
According to a preferred embodiment of the present invention; The method that eco-friendly is used to reclaim pyridine and/or its verivate is provided; This method adopts the organic solvent of environmental sound; Wherein this method comprises from containing the manufacturing RM recovery ammonia of pyridine and/or its verivate and other lower boiling and high boiling by product and ammonia; Use said SX gained to contain the aqueous substance of pyridine and/or its verivate, the organic phase that forms by the said solvent that contains pyridine and/or its verivate from aqueous phase separation and reclaim pyridine and/or its verivate from organic phase through fractional distillation.
According to another embodiment of the invention, the method that eco-friendly is used to reclaim pyridine and/or its verivate is provided, this method with an organic solvent, wherein said solvent is the solvent of environmental sound, it is selected from the Class III solvent according to the ICH guide.
According to another embodiment of the invention, the method that eco-friendly is used to reclaim pyridine and/or its verivate is provided, this method with an organic solvent, wherein said solvent is preferably selected from alkyl acetate.
According to another embodiment of the invention; The method that eco-friendly is used to reclaim pyridine and/or its verivate is provided; This method is used said organic solvent alkyl acetate, and wherein said method is efficient recovery and the said solvent of recycling from water and the refuse that comprises the corresponding alkanol that obtains the said alkyl acetate of part and this method in addition.
According to another embodiment of the invention; The method that eco-friendly is used to reclaim pyridine and/or its verivate is provided; This method is used the organic solvent of environmental sound; Wherein this method is included in and reclaims in this method employed solvent in the organic process of distillation extraction and in the method that reclaims pyridine and/or its verivate, reuse them.
According to another embodiment of the invention; The method that is used to reclaim pyridine and/or its verivate to eco-friendly is provided; This method is used alkyl acetate; Wherein this method comprises the gained alkanol esterification that the hydrolysis alkyl acetate is produced, and it is reclaimed with unreacted alkyl acetate, and re-uses in the method.
According to another embodiment of the invention; The method that eco-friendly is used to reclaim pyridine and/or its verivate is provided, and this method is used alkyl acetate, the wherein various alkanols of this method efficient recovery; This alkanol is owing to the highly basic system is degraded, and re-uses during with its in the method esterification.
Detailed Description Of The Invention
This specification sheets is supported claims, and claims particularly point out and the content (it is considered to the present invention) that clearly requires to be protected, and can expect that the present invention can more easily understand through the embodiment that reads following detailed description and research and comprise.
Current social along with ecological problem, i.e. the increase of pollution, Global warming etc., the emphasis in the industry is that not only economic means also is green method.Therefore, the present state of affairs becomes needs combination economy and ecological principle in the method for any research and development.Therefore; The present invention has accomplished these purposes; Its provide aspect the most widely from aqueous substance and/or its make RM extraction pyridine with and/or the method for its verivate, and do not use highly deleterious solvent such as benzene and substantial contribution and the disagreeableness method of operation like the use carbonic acid gas.
Embodiment disclosed by the invention relates to the method that reclaims pyridine and/or its verivate, and it has the advantage of the solvent of avoiding operating unsafe solvent such as benzene and using during recycling is reclaimed effectively.And the inventive method relates to uses the suitable solvent of industry so that it becomes comparatively safe, friendly more and economic operation.Therefore, the present invention has overcome the shortcoming and the challenge of former disclosed method.
According to the present invention; Provide from water-based RM and/or its and make the method that RM reclaims pyridine and pyridine derivate, it uses alkyl acetate (according to the Class III solvent of ICH guide) to replace hazardous solvent (like benzene) (according to the Class I solvent of ICH guide).Alkyl acetate is nontoxic with environmentally acceptable as solvent phase than benzene.Use alkyl acetate recovery pyridine and pyridine derivate except the direct investment income, reduced environmental hazard, the related cost of environmental protective measure, increased occupational safety and saved the harmful waste processing costs.
According to the present invention, provide from water-based RM and/or its and make the method that RM reclaims pyridine and/or pyridine derivate, it uses the solvent to eco-friendly, and it basically is non-solvent with its verivate for excellent solvent but to water to pyridine.After extraction was accomplished, the gained extract carried out fractional distillation, and it is removed solvent fully and makes pyridine and/or pyridine derivate is in anhydrous basically state.
According to the present invention, the method that this paper uses is made pyridine and/or its verivate that RM separates anhydrous basically state from its aqueous substance and/or its." making RM " that this paper uses is meant that the RM that in pyridine and/or its verivate manufacturing processed, obtains, wherein said manufacturing material can comprise pyridine, β picoline, ammonia, aliphatic amine, aldehyde and aldehyde radical organic impurity, other monoalkyl pyridines, dialkyl group pyridines, trialkyl pyridines or other Unidentified heavy organic substance (heavy organic materials).
The disclosed the preferred embodiments of the invention of this paper have been described from aqueous substance and/or its and have been made the method that RM separates pyridine and/or pyridine derivate, and this method can more easily be understood from following detailed Description Of The Invention and method flow diagram.
The present invention provides the improved method of separating pyridine and pyridine derivate; It comprises at first at barometric point and to keep the still temperature be to reclaim ammonia from making RM under 85-95 ℃; To be implemented in minimum possible ammonia (ideal＜1.6%) in the RM; Because the ammonia of high level reduces the recovery of solvent, so this method is economical.This recovery also can be carried out in a vacuum.
Reclaiming the RM that obtains behind the ammonia extracts with the preferred alkyl acetate of organic solvent.The alkyl acetate that this paper uses is preferably selected from ETHYLE ACETATE, n-propyl acetate, isopropyl acetate, methyl acetate etc.Be preferably ETHYLE ACETATE.This is recovered in the batch extraction system and carries out.Yet this recovery also can be carried out in the continuous extraction system.The RM that will contain pyridine and picoline and other high boiling pyridine bases and some lower boiling compositions stirs with solvent through any known existing method.After about 30 minutes, stop to stir two-layer in stirring at room to isolate.Water layer is used to analyze pyridine and picoline content.To the water layer that contains alkyl acetate repeat once more this method up to pyridine and/or pyridine derivate reach at the content of water layer [stream-1] in (stream-1)＜0.1%.
Then gained water layer use separation column under barometric point is heated.Front-end volatiles (precut) are made up of two-layer, and it is separated, but and do not contain the residuum any processor of pyridine bases, perhaps through incinerating or through in other method, suitably using.The organic layer of front-end volatiles, it is rich in alkyl acetate/alkanol, is alkyl acetate according to remaining the alkanol esterification in the method for commercial foundation, extracts then to carry out recycling.What the water layer of front-end volatiles was suitable incinerates.
According to aforesaid method of the present invention, organic layer uses the separation column distillation.Also additional have dean stark device to be used to reclaim water layer.A spot of water is present in organic layer, and this is because the solvability of water in alkyl acetate.Front-end volatiles are made up of organic layer and water layer.Water layer [stream-2] mixes with the water layer [stream-1] that final extraction back obtains, and is used for reclaiming alkyl acetate/alkanol through above-mentioned distillation technique.After separating front-end volatiles, reclaim the cut-1 [stream-4] that comprises alkyl acetate and some alkanols.Keep middle runnings (intercut) amount so that in the alkyl acetate of the used recovery of next batch extraction alkanol preferably remain on＜0.2%.If amount＞0.2% of the alkanol in the cut 1 [stream 4] adds this cut and mixed being incorporated in the esterification process of stream-3 in the water washing stage, be used to be recovered in the alkyl acetate of extraction stages recycling.
Reclaiming the lasting distillation in front-end volatiles and cut-1 back to reclaim solvent, this solvent can be used for the next batch extraction.Surplus materials after the solvent recuperation uses separation column further to distill according to the method for having set up in the industry step by step, reclaims the pyridine and the picoline of required specification then.
Further, the present invention specifies through following examples.The embodiment of this paper is used for explaining the present invention rather than restriction the present invention.
Embodiment-1
Reduce ammonia from pyridine, beta-picoline RM
2500gm pyridine, beta-picoline are made RM [% pyridine-13.49, % beta-picoline 5.49, %NH
37.80; Fatty amine, aldehyde and aldehyde radical organic impurity, other monoalkyl pyridines, dialkyl group pyridines, trialkyl pyridines or other Unidentified heavy organic substance] to put in 5 liters of round-bottomed flasks, this flask is equipped with two-sided condensing surface (condenser) and NH
3Washer.This RM is heated to the 85-95 ℃ of NH in pyridine-beta-picoline RM
3Content reaches＜and 1.6%.NH
3After the recovery, obtain 2300gm pyridine, beta-picoline RM [% pyridine-14.70, % beta-picoline 5.93, %NH
31.53], it is fit to use ethyl acetate extraction.
Embodiment-2
NH
3After the recovery, use ETHYLE ACETATE from pyridine, beta-picoline RM extraction pyridine and beta-picoline
With fresh ETHYLE ACETATE [295.0gm] and pyridine, beta-picoline RM [575gm, % pyridine-14.70, % beta-picoline 5.93, %NH
31.53; Fatty amine, aldehyde and aldehydes organic impurity, other monoalkyl pyridines, dialkyl group pyridines, trialkyl pyridines or other Unidentified heavy organic substance] to put in two liters of round-bottomed flasks, this flask is equipped with thermocouple sheath and two-sided condensing surface.This material stirring at room 30 minutes, is transferred to separating funnel with layering with it then.Separate each layer and water layer and be used to analyze pyridine and beta-picoline content.Again load this water layer and fresh ETHYLE ACETATE (135gm) and repeat this process.After total coextration 9 times, pyridine and the beta-picoline in the water layer reaches＜0.1% [stream-1] [ETHYLE ACETATE 295gm x 1 and 135gm x 8].
Embodiment-3
The solvent that recovery is used to extract
The organic layer [1503gm] of extraction is equipped with among 5 liters of RBF of glass column [high 2m, diameter 25mm fill with the S.S. structured packing], reflux head (reflux divider) and dean stark device, to separate water layer.This material slowly is heated to 70 ± 5 ℃ of reflux temperatures and kept backflow 2-4 hour.Behind the system stability, begin to isolate and contain two-layer front-end volatiles.Water layer [stream-2] comprises water and ethanol (1-5%) and ethamine, and organic layer [stream-3] comprises the ethanol (2-5%) of ETHYLE ACETATE (95%) and trace.And, the middle runnings [stream-4] of isolating ETHYLE ACETATE (90-95%), it comprises ethanol (2-5%).Further after the distillation, isolate ETHYLE ACETATE [test 98%, ethanol＜0.2%] with recycling in extracting system.Surplus materials is substantially free of water, and its method of having set up according to industry is used the distillation of fractional distillation technology, with pyridine and the β picoline that separates required specification.
Embodiment-4
Reclaiming ETHYLE ACETATE from waste streams is used in extracting system recycling
To flow-1 and stream-2 combine and use separation column [a meter long, and diameter 25mm fills with the S.S. structured packing] to distill.Front-end volatiles are collected into the near-bottom temperature up to 90-100 ℃.It is made up of two-layer.Organic layer comprises ETHYLE ACETATE (60-80%) and ethanol (15-30%) [stream-5].The water layer that contains 2-4% ETHYLE ACETATE and 1-2% ethamine can incinerate.The remaining aqueous substance that does not contain pyridine bases can be disposed through incinerating easily, or uses in suitable procedure for diluting purpose.To flow-5 recycling after the esterification to be used for extraction.
Embodiment-5
The recycling research of the ETHYLE ACETATE that reclaims:
Be the recycling of research ETHYLE ACETATE, after carrying out essential processing with fresh ethyl according to the method described above, obtain similar turnout (capacity) more than 3 parts.In a word, 2500gm pyridine, beta-picoline RM are used the 1813gm fresh ethyl.Wherein 1183gm ETHYLE ACETATE (measure 98%, EtOH＜0.2%) reclaims from the organic substance of extraction, with it in extraction stages recycling.Comprise that 1246gm ETHYLE ACETATE reclaims according to the method described above altogether from stream-1 to 5 recovery, and with it in extraction stages recycling.Solvent loss can further minimize when extraction is carried out according to the operate continuously mode, because the primary solvent loss is because the treatment losses in batch mode.
Although with reference to some preferred embodiment detailed description, should understanding, the present invention the invention is not restricted to this concrete embodiment.On the contrary, according to open (it is described and puts into practice preferred forms of the present invention at present) of the present invention, those skilled in the art can carry out many modifications and variation and not depart from scope of the present invention and essence.
Claims (5)
1. to the method that from aqueous substance and/or their manufacturing RM, reclaims pyridine and/or its verivate of eco-friendly, this method comprises:
In said method, use alkyl acetate;
Reclaim pyridine and/or its verivate; With
Mode to reclaim in the refuse that said alkyl acetate is produced from organic phase, water and this method is carried out said method.
2. according to the process of claim 1 wherein that this method comprises:
Handle said aqueous substance and/or said manufacturing RM to obtain organic phase and water with said alkyl acetate;
Separating obtained organic phase and water;
Distill said organic phase with acquisition pyridine and/or its verivate, and said alkyl acetate reclaims through the refuse that produces in distillation and said water of esterification and the said method in addition; With
The said alkyl acetate that reclaims in the said method of recycling.
3. according to claim 1 or 2 each methods, wherein said alkyl acetate is an environmental sound according to the Class III of ICH guide.
4. according to claim 1 or 2 each methods, wherein said alkyl acetate is selected from ETHYLE ACETATE, n-propyl acetate, isopropyl acetate and methyl acetate.
5. according to the method for claim 4, wherein said alkyl acetate is an ETHYLE ACETATE.
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| Application Number | Priority Date | Filing Date | Title |
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| IN2021DE2006 | 2006-09-12 | ||
| IN2021/DEL/2006 | 2006-09-12 | ||
| PCT/IN2006/000456 WO2008032334A1 (en) | 2006-09-12 | 2006-11-17 | Eco-friendly process for recovery of pyridine and/or its derivatives |
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| CN101511788B true CN101511788B (en) | 2012-07-18 |
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| US (1) | US8057643B2 (en) |
| JP (1) | JP2010503661A (en) |
| CN (1) | CN101511788B (en) |
| GB (1) | GB2454136B (en) |
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| WO (1) | WO2008032334A1 (en) |
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| CN101973931B (en) * | 2010-10-28 | 2012-05-23 | 攀钢集团钢铁钒钛股份有限公司 | Method for extracting pyridine from ammonium sulfate mother liquor |
| CN103044319B (en) * | 2013-01-25 | 2014-09-24 | 山东元利科技股份有限公司 | Method for extracting 2-picoline and 3-picoline from coking crude benzene |
| CN111138347B (en) * | 2019-12-31 | 2023-05-12 | 鹤壁市赛科化工有限公司 | Industrial method and device for water diversion of vinyl pyridine compounds |
| CN116332836B (en) * | 2022-07-28 | 2024-03-26 | 四川熔增环保科技有限公司 | Method for recovering pyridine waste solvent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4364869A (en) * | 1980-09-12 | 1982-12-21 | Chemische Werke Huls A.G. | Process for producing alkyl esters of saturated aliphatic carboxylic acids |
| US5100514A (en) * | 1991-03-01 | 1992-03-31 | Lloyd Berg | Separation of pyridine from water by extractive distillation |
| US6346623B1 (en) * | 1998-06-22 | 2002-02-12 | Dsm Fine Chemicals Austria Nfg Gmbh & Cokg | Method for producing substituted pyridine-carboxylic acids |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2058435A (en) * | 1936-10-27 | Method of dehydrating pykdjine | ||
| US4237300A (en) * | 1975-12-09 | 1980-12-02 | Merck & Co., Inc. | Certain 6-substituted-2-pyridinamines |
| US4404388A (en) * | 1981-08-14 | 1983-09-13 | Ciba-Geigy Corporation | Process for producing 2-chloropyridines |
| DE3631679A1 (en) * | 1986-09-18 | 1988-03-24 | Basf Ag | METHOD FOR SEPARATING PYRIDINE FROM MIXTURES OF PYRIDINE AND ISOVALERIAN ACID METHYL ESTER |
| US5208342A (en) * | 1992-03-30 | 1993-05-04 | Hoechst Celanese Corporation | Conversion of pyridine-2,3-dicarboxylic acid esters to cyclic anhydrides |
| JP3037024B2 (en) * | 1992-06-10 | 2000-04-24 | 富士写真フイルム株式会社 | 5-acyl-4,5,6,7-tetrahydrothieno [3,2-c] pyridine-2-carboxylic acid derivative and method for producing the same |
| US5364941A (en) * | 1992-06-10 | 1994-11-15 | Fuji Photo Film Co., Ltd. | 5-acyl-4,5,6,7-tetrahydrothieno (3,2-C)pyridine-2-carboxylic acid derivative and process for producing the same |
| JPH07215939A (en) * | 1994-02-04 | 1995-08-15 | Mitsubishi Chem Corp | Separation of 2-chloro-5-aminomethylpyridine |
| WO1995033725A1 (en) * | 1994-06-03 | 1995-12-14 | John Wyeth & Brother Limited | Novel processes and intermediates for the preparation of piperazine derivatives |
| FI101294B (en) * | 1996-10-30 | 1998-05-29 | Valtion Teknillinen | Method for separating pyridine or pyridine derivatives from aqueous solutions |
| EP1424328B1 (en) * | 2002-11-28 | 2005-11-09 | Jubilant Organosys Limited | Process for producing 4-dimethyl amino pyridine (4-DMAP) |
| US7348435B2 (en) * | 2004-10-18 | 2008-03-25 | Jubilant Organosys Limited | Process for producing cyanopiperidine |
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- 2006-11-17 CN CN2006800558238A patent/CN101511788B/en not_active Expired - Fee Related
- 2006-11-17 GB GB0902647A patent/GB2454136B/en not_active Expired - Fee Related
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- 2006-11-17 JP JP2009527962A patent/JP2010503661A/en active Pending
- 2006-11-17 WO PCT/IN2006/000456 patent/WO2008032334A1/en active Application Filing
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4364869A (en) * | 1980-09-12 | 1982-12-21 | Chemische Werke Huls A.G. | Process for producing alkyl esters of saturated aliphatic carboxylic acids |
| US5100514A (en) * | 1991-03-01 | 1992-03-31 | Lloyd Berg | Separation of pyridine from water by extractive distillation |
| US6346623B1 (en) * | 1998-06-22 | 2002-02-12 | Dsm Fine Chemicals Austria Nfg Gmbh & Cokg | Method for producing substituted pyridine-carboxylic acids |
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| Publication number | Publication date |
|---|---|
| GB2454136B (en) | 2011-11-30 |
| CN101511788A (en) | 2009-08-19 |
| US8057643B2 (en) | 2011-11-15 |
| TW200812966A (en) | 2008-03-16 |
| GB0902647D0 (en) | 2009-04-01 |
| GB2454136A (en) | 2009-04-29 |
| WO2008032334A8 (en) | 2008-09-04 |
| JP2010503661A (en) | 2010-02-04 |
| WO2008032334A1 (en) | 2008-03-20 |
| US20100041894A1 (en) | 2010-02-18 |
| TWI370119B (en) | 2012-08-11 |
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